Pigments of the perylenetetraacetic carboxylic acid diimide series

ABSTRACT

PERCYLENETETRAACETIC CARBOXYLIC ACID DIIMIDES ARE PREPARED BY CONDENSING PERYLENE - 3,4,9,10 - TETRACARBOXYLIC ACID WITH 2-AMINOTHIADIAZOLES. THE NEW PERYLENE DERIVATIVES ARE USED AS PIGMENTS.

Patent lice 3 631 048 PIGMENTS OF THE TER YLENETETRAACETIC CARBOXYLIC ACID DIIMIDE SERIES Georg Anton Klein, Bottmingen, Basel-Land, Switzerland,

3,631,048 Patented Dec. 28, 1971 pressure vessels, preferably at 200 to 230 C. Used, if

necessary, for the condensation process are condensation,

assign to Ciba Geigy AG, Basel, Switzerland 5 of organic carboxylic acids such as, e.g. zinc formate, zinc No Drawing. Filed July 14, 1970, Ser. No. 54,858 etate, zmc stearate, cadmium acetate, or the ZlIlC salts Int CL 307 91/ 2 of benzoic acid, phthalic acid, phenylacetic acid, and n1co U.S. Cl. 260-281 6 Claims tinic acid. Particularly suitable for the purpose is zinc acetylacetonate; in the presence of this the reaction pro- 10 ceeds rapidly and in good yield. In general, 0.1 to 1 mole ABSTRACT OF THE DISCLOSURE of zinc acetylacetonate per mole of perylenetetracarlPerylenetetraacetic carboxylic acid diimides are preboxyhc used in the condensafiqn Process; but it is pared by condensing perylene 3,4,9,l0 tetracarboxylic Posslb1e to f e densation agent The reacid with Z-aminothiadiazoles. The new perylene derivaf Proceeds satlsfactoflly however even Wlthout h fives are used as pigments 15 addition of a condensation agent. Moreover, the pigments can also be produced by the melting together of the two constituents; the obtained pigment is then washed DESCRIPTION OF THE INVENTION with dilute potassium hydroxide solution and with water, and afterwards dried and ground. It preferably undergoes The invention concerns new compounds of the peryla further grinding in the presence of salts such as calenetetracarboxylic acid diimide series, their use for the cium chloride, whereupon it is finally separated from pigmenting of high-molecular organic material, and the the salt, compositions thereof. By condensing per mole of perylenetetracarboxylic It has been found that compound of Formula I acid-3,4,9,10-dianhydride, 1 mole each of thiadiazoles O O t t N-N NN Iii-0 ON N(/ e n' \S/ S/ (1) ii wherein varyingly substituted in the 5-position, unsymmetrically R and are identical or different, and each represent substituted perylenetetracarboxylic acid diimides of Forhydrogen, an alkyl group having 1-4 carbon atoms, mula I are Obtamed' a phenyl group optionally substituted by chlorine; chlonew compouflds accqdmg to the mvenFlon are Tine, the mercapto group, the amino group, or the suitable for the dyelng of high-molecular organic matephenylamino group, 40 rials, e.g. for the pigmentmg of lacquers, also metal-effect lacquers, plastlc masses, such as hard or plast1c1ser-conare deeply coloured and br1ll1ant bluish red pigments mining polyvinyl chloride, polyethylene polypropylene, which possess excellent fastness properties, such as fastpolyurethane, polycarbonate, polystyrene, l l i. HESS to g migration, cross'lacquenng, heat trile, for the spinning-dyeing of synthetic fibres, or as VeIltS- Such Pigments Very 'vahfable comm?rclany, printing ink. The pigment can be used direct, or after a d a e Sought after Slnce 0f the P know? Plgments being converted into a finely dispersed form. The comof similar chemical structure, only a few satisfy the repounds can also be used as vat d t ff In h f ll quirements with regard to fastness, and none attain the ing examples, the temperature is given in O Q brilliance and colour strength of the pigments according E 1 1 to the invention. xamp e When R and R in Formula I are identical, then the (1,1) N,N' bis (2 methyl 1,3,4 thiadiaz01y1-5)- pigments are symmetrically formed, which is preferred. perylene-3,4,9,l0 tetracarboxylic acid diimide-In a four- Where R denotes an alkyl group with 1 to 4 carbon atoms, necked flask of 350 ml. content, fitted with thermometer, it is generally the methyl group, the ethyl group, the stirrer and fractionating column, and containing 150 g. propyl group, the isopropyl group, or the butyl group, of quinoline, an amount of 8 g. of perylenetetracarpreferably however the methyl group. Also preferred 1s boxylic acid-3,4,9,IO-dranhydnde 1s stirred in; the whole moreover a pigment whereby R denotes the phenyl group, 1s heated to 237, until pure qulnoline distils over; to the an 0- or p-chlorophenyl group or the amino group. suspension at 200 are slowly added 4.6 g. of 2-am1no-5- h new i nt are produced by condensing perylmethylthiad1azole-1,3,4, and SlilIllIlg is maintained at 220 ene-3,4,9,IO-tetracarboxylic acid, or a reactive acid deor five h s. T e t e S e 0016d t0 9, lrivative thereof, with two identical or different 2aminotefed 01f under Suctlon; and cfystalllne resldlle ls thiadiazoles of Formula washed with 200 ml. of hot quinolme, 200 ml. of glacial acetic acid, and 50 ml. of methyl alcohol. After being dried in a vacuum of 15 mm. Hg at 60, the welght of the C NHB residue is 12 g.

\ These 12 g. of N,N-bis-(Z-methyl-1,3,4-thiadiazolyl-5)- S (H) perylene-3,4,9,IO-tetracarboxylic acid diimide are ground wherein R has the meanings given in Formula I. in a vibrating mill of one litre capacity with 3.6 kg of Condensation is preferably performed in high-boiling steel balls having a diameter of 1.5 cm., 60 g. of calc1um solvents, such as quinoline, trichlorobenzene, diphenylchloride, and 4.5 g. of special petroleum which boils beene oxide, diphenyl, or mixtures thereof. In the case of tween 165 and 200. The ground material is afterwards using pyridine as the solvent, it is advantageous to condense at temperatures above the normal bOlllIlg point, in

suspended in 500 ml. of 1 N hydrochloric acid; the suspension is stirred at during one hour, and filtered ofl under suction; the residue is then washed with one litre minium hydroxide, 60 g. of linseed-oil varnish of medium of hot water, and dried in a vacuum of 15 mm. Hg at viscosity, and 0.2 g. of cobalt linoleate are mixed on a 60. In this manner are obtained 11.1 g. of a very pure three-roller mill, and ground. A printing ink is obtained bluish red pigment of high colour strength and having which gives bluish red paper printings having good fastexcellent fastness to light, migration, cross-lacquering, mess to light. heat, and solvents. Example 4 If, instead of the applied 2-aminotl1iadiazole-1,3,4 having a methyl group in the 5-position, equivalent amounts of such 2-aminothiadiazole-1,3,4 which contain in the 5- position the following substituents R of Formula II are condensed with perylenetetracarboxylic acid-3,4,9,l0-dianhydride, then likewise are obtained pigments of Formula I, wherein R and R are identical, possessing similar An amount of 1 g. of the pigment according to Example 1.1, and 5 g. of titanium dioxide are added to 100 g. of a stoving lacquer consisting of 58.5 g. of a 60% solution of a coconut-oil fatty acid modified alkyd resin in Xylene, 23 g. of a 65% solution of a melamine lacquer resin in butanol, 17 g. of xylene and 1.5 g. of butanol. After 48 hours grinding of the mixture in a ball mill, the

propertles: thus pigmented lacquer is sprayed onto a cleaned metal surface. The bluish red coating has, after stoving at 120, Colour of Pigment Substituentin 5-position thepigment; a very good fastness to light, cross-lacquering and to 1.2 Ethyl group BllllSll red. Weather 1.3 Islopropyl group 120. Example 5 1.4. Pieny group 0. 1.5 o Clilorophenyl group. D0. 20 An amount of 6.7 g. of polyvinyl chloride powder (suspension polymerisate), 33 g. of dioctylphthalate, 2 g. of 1. Chlorine D0. dibutyl tin dilaurate, 0.3 g. of a stabiliser based on phosphate, and 0.7 g. of the pigment produced according to 1.10 Do. 1.11 Amino group D Example 1 by condensation of perylenetetracarboxylic Phmymmmo glow Blown acid 3,4,9,10 dianhydride and 2-amino-5-methylthiadiazole 1,3,4, is mixed and then processed for 15 minutes on mixing rolls heated to 160. A sheet of 0.4 mm. thickness (2.1) N-[Z-(o-chlorophenyl) 1,3,4 thiadiazol-5-yl]- is afterwards produced on a calendering machine. The N-[2-methyl-1,3,4-thiadiazol 5 yl] perylenetetracarbluish red dyeing of the sheet is heat-resistant and has boxylic acid-3,4,9,10-diimide.-Into a flask with stirrer fastness to migration and light.

Example 2 and with fractionating column are placed 150 g. of quino- What I claim is: line, 0.26 g. of zinc acetonylacetate, 8 g. of perylenetetra- 1. Compounds of the. Formula I O O RC CN\ /N-C C-R --o u U u carboxylic acid-3,4,9,IO-dianhydride, 4.4 g. of 2-amino-5- wherein R and R are identical or different, and each (o-chlorophenyl)-thiadiazole-1,3,4 and 2.4 g. of 2-aminorepresent hydrogen, an alkyl group having 14 carbon S-methylthiadiazole-1,3,4. atoms, an unsubstituted phenyl group or a phenyl group This mixture is vigorously Stirred heated to 2200, which is substituted by chlorine; chlorine, the mercapto maintained for two hours at this temperature, cooled to 5 group, the ammo group of the Phenylammo p- 150, and filtered. The residue is washed three times with 2. A compound according to claim 1 which is N,N'-bis- 100 ml. of quinoline each time, once with 100 ml. of (2 methyl 1,3,4-thiadiazolyl-5)-perylene-3,4,9,10-tetraglacial acetic acid, three times with 100 ml. of methanol carboxylic acid diimide. each time; and is then dried at 60 in a container under 3. A compound according to claim 1 which is N,N'-bisa pressure of 15 mm. Hg. After 12 hours, the obtained (2 phenyl 1,3,4-thiadiazolyl-5)-perylene-3,4,9,IO-tetra- 12.4 g. of crystals are ground for two hours in a vibratcarboxylic acid diimide. ing mill of one litre capacity and filled with 3.6 kg. of steel 4. A compound according to claim 1 which is N,N-bisballs of 1.5 cm. diameter; together with 70 g. of calcium (Z-o-chlorophenyl-1,3,4-1hiadiazolyl-5 )-perylene-3,4,9,10- chloride and 4 g. of special petroleum (B.P.=165200). tetracarboxylic acid diimide.

After one hour of stirring in 500 ml. of 1 N hydrochloric 5. A compound according to claim 1 which is N,N'-bisacid at 80, filtration and drying at (vac the (2-p-chlorophenyl-1,3,4-thiadiazolyl 5)-perylene-3,4,9,l0-

ground material is obtained consisting of 11.7 g. of N- tetracarboxylic acid diimide. [2-(o-chlorophenyl)-1,3,4-thiadiazol 5 yl]-N-[2-meth- 6. A compound according to claim 1 which is N,N'-bisyl-1,3,4 thiadiazol 5 yl]-perylenetetracarboxylic acid- (2 amino 1,3,4-thiadiazolyl-5)-perylene-3,4,9,10-tetra- 3,4,9,10-diimide, a somewhat bluish red pigment, but 60 carboxylic acid amide. otherwise possessing similarly good properties to those of the pigment described in Example 1.1. 0 References Cited If, instead of 2-amino-5-(o=chlorophenyl)-th1ad1azole- UNITED STATES PATENTS 1,3,4 equivalent amounts of 2-aminothiadiazoles having the following substituents in the 5-position are used, then 3,332,931 7/1967 Bra n 250 .2g X pigments possessing similar properties are obtained: 3,357,983 12/ 1967 Weener et al 260-281 3,546,222 12/1970 Irving et al 260-249.6 n me filliffiiiiiti $3,333.31 FOREIGN PATENTS 2,2 p-Chlorophenyl BlulSll red. 894,859 96 Great Britain 26U2l8 2.3 Phenyl Do.

DONALD G. '-DAUS, Primary Examiner Example 3 4 g. of N,N-bis-(5 phenyl) 1,3,4 thiadiazolyl-2)- perylenetetracarboxylic acid-3,4,9,10-diimide, 36 g. of alu- 834; l06-288 O; 26()37 N, 37 NP, 302 D 

